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The science base that underlies modelling and analysis of machine reliability has remained
substantially unchanged for decades. Therefore, it is not surprising that a significant
gap exists between available machinery technology and science to capture degradation
dynamics for prediction of failure. Further, there is a lack of a systematic technique for the
development of accelerated failure testing of machinery components. This article develops a
thermodynamic characterization of degradation dynamics, which employs entropy, a
measure of thermodynamic disorder, as the fundamental measure of degradation; this
relates entropy generation to irreversible degradation and shows that components of
material degradation can be related to the production of corresponding thermodynamic
entropy by the irreversible dissipative processes that characterize the degradation. A
theorem that relates entropy generation to irreversible degradation, via generalized thermo-
dynamic forces and degradation forces, is constructed. This theorem provides the basis of a
structured method for formulating degradation models consistent with the laws of thermo-
dynamics. Applications of the theorem to problems involving sliding wear and fretting wear,
caused by effects of friction and associated with tribological components, are presented.
Keywords: thermodynamic entropy; degradation; ageing; wear; friction; tribology
1. Introduction
2. Formulations
(a ) Definitions
A dissipative degradation process pi is the minimum 0
group of physical
sub-processes for which the entropy production S_ i produced by the group is
0
non-negative, i.e. S_ i R 0.
A degradation mechanism is a sequence of one or more dissipative degradation
processes pi (iZ1, 2, ., m) that degrade or impair the functionality of a material
or material body.
A degradation measure wZw{p1, p2, ., pi , ., pm} is a non-negative, non-
decreasing continuous function, differentiable in one or more variables pi ,
associated with a degradation mechanism.
(b ) Thermodynamics of degradation
Suppose a degradation mechanism consists of iZ1, 2, ., n dissipative
processes pi , where each pi Z pi ðzji Þ describes an energy, work or heat characteristic
Since the second law mandates non-negative entropy generation, signs in equation
(2.4) of multiplying factors must be identical, i.e. sgnðXij ÞZ sgnðJij Þ. Equations
(2.3) and (2.4) share rate factors J ji . Irreversible thermodynamics considers forces
Xij as drivers of flows J ji . Each J ji can depend on all forces (De Grote & Mazur 1984)
and intensive quantities (e.g. temperature T ) associated with the dissipative
process via (Bejan 1988)
X
J j Z J j ðX 1 ; X 2 ; .; TÞ z Lq j X q ; ð2:6Þ
q
where subscript i was dropped in equation (2.6) for clarity. For systems near
equilibrium or stationary, relation (2.6) is invertible (Hillert & Agren 2006) and
usually assumed linear (Bejan 1988). Non-negative entropy production demands
symmetric, positive definite Lq j. Applications of equations (2.4) and (2.5) have
explained diverse phenomena—thermoelectric effect, diffusion (Bejan 1988),
reactions (Kondepudi & Prigogine 1998) and phase changes, amongst others—
and have given an alternate derivation of Kirchhoff’s voltage law for resistive
networks (Županović et al. 2004).
which exists, since Xij s0 except when the system is not degrading. Equation (2.5)
was used in equation (2.7). The last term in equation (2.7) means vw/vS 0
with process pi active, which suggests Bi measures how entropy generation and
degradation interact on the level of processes pi , rather than process variables zji .
Since increments of degradation are non-negative, coefficients BiR0. Finally, if
equations (2.5) and (2.7) are applied to equations (2.3) and (2.4), then
! !
X j j X vw vpi vzj X vw=vpi vS 0 vpi vzj
i i
w_ i Z Yi Ji Z j Z 0 =vp j
j j
vpi vz i
vt j
vS i vp i vz i
vt
X 0
Z Bi Xij Jij Z Bi S_ i : ð2:8Þ
j
(iii) the generalized ‘degradation forces’ Yij are linear functions Yij Z Bi Xij
of the generalized ‘thermodynamic forces’ Xij , and
(iv) the proportionality factors Bi are the degradation coefficients given by
equation (2.7).
(e ) Conservation of energy
All systems must obey conservation of energy, stated by the first law of
thermodynamics X
dE Z dQKdW C hk dNk ; ð2:9aÞ
where E is internal energy; Q and W are heat flow and work across the boundary of
the relevant control volume; and hk and Nk are chemical potential and number of
moles of species k. A change in entropy,
dS Z dS 0 C dSe ; ð2:9bÞ
consists of a reversible change dSe from entropy flow, and an irreversible change
from entropy generation dS 0 . We note
P that entropy flow arises from heat transfer
via heat flow dQ and matter flow h k d e Nk ,
X
T dSe Z dQ C h k d e Nk : ð2:9cÞ
A change in the number of moles,
dNk Z d 0 Nk C d e Nk ; ð2:9dÞ
consists of a chemical reaction term d 0 Nk and a matter transport term deNk . At
equilibrium, a system’s entropy is maximum and entropy production ceases:
dS 0 /dtZ0 (Kondepudi & Prigogine 1998). A system produces entropy (dS 0 /dtO0)
until equilibrium. Stationary systems have dEZ0 and dSZ0.
Our interest is the irreversible effects of dissipation caused by work of
non-conservative forces. This P dissipated work must eventually diffuse through
heat flow dQ and/or mass flow hk dNk , as an entropy flow dSe/dt. Via equation
(2.9a)–(2.9d ), the irreversible entropy produced can be linked to the work
dissipated (Frederick & Chang 1965; Klamecki 1984; Bejan 1988). Open systems
demand balancing flows of entropy, heat, work, energy and mass over a control
volume about the degrading body or system, to construct open system counterparts
of entropy generation equation (2.4), and possibly degradation equation (2.3).
If needed, via equation (2.6), relate rates Jij to thermodynamic forces Xij .
3. Applications
This work is dissipated within the control volume. For sliding of ductile metals,
Rigney & Hirth (1979) identified the dominant dissipative process p to be work of
plastic deformation. Let us assume that (i) rubbing is at steady speed and force,
and is a stationary process. In other words, for steady-state sliding, changes to the
internal energy dE and entropy dS contained within the small wear control volume
that surrounds the sliding surface and near interior regions of the wearing
P body are
small. (ii) Energy transport effects of material loss are small, hk d e Nk is
negligible compared with other terms in equation (2.9c), thus permitting us to treat
the system as closed. (iii) There are no chemical reactions occurring. (iv) All
friction work is dissipated within the control volume, i.e. dpZKdW. Applying
assumptions (i)–(iv) to equation (2.9a)–(9c) yields
dW Z dQ Z T dSe ZKT dS 0 :
The rate of irreversible entropy generated due to friction can be obtained as follows:
dS 0 vS 0 vp vx Fm dx
Z Z ; ð3:2aÞ
dt vp vx vt T dt
where contact temperature T arose in equation (3.2a) from vS 0 /vpZ(dS 0 /dW )
(dW/dp)Z1/T. For dS 0 /dtR0, since TR0, Fm and dx/dt must have the same signs
in the relevant free body diagram for the slider; this is consistent with the friction
force always opposing the direction of the sliding velocity.
Comparing equation (3.2a) with equation (2.4),
J Z dx=dt; ð3:2bÞ
zZx, dp/dxZFm and thus
X Z vS 0 =vpðvp=vzÞ Z F =T: ð3:2cÞ
Also, JZJ(X ) by equation (2.6) is consistent with the observed friction force
dependency on sliding speed and temperature.
Applying equations (3.1) or (2.3) yields
dw BFm dx Bm dx
w_ v Z v Z YJ Z BXJ Z Z N ; ð3:2dÞ
dt T dt T dt
where wv represents wear volume and YZBmN/T.
Constant B can be measured via equation (2.7), i.e. BZdw/dS 0 , using dS 0 ZKdSe
for a stationary process.
Doelling et al. (2000) conducted extensive experimental measurements of wear
in an apparatus where a stationary copper specimen was in boundary lubricated
contact with a rotating steel cylinder. They reported a series of measurements to
establish relationship between normalized wear as a function of normalized entropy
flow. The entropy flow, the negative
P of entropy production for a stationary process,
was calculated using SM Z M DQ ðlÞ =T ðlÞ , where DQ(l ) is the heat input to the
slider during the lth time interval and T (l ) is the corresponding average absolute
surface temperature of the stationary rider on the rotating cylinder. Both
temperature and wear rates were measured and the slope of normalized wear
plotted versus the normalized entropy flow was evaluated. This slope is precisely
the degradation ratio B defined in §2c, equation (2.7).
Having determined B, equation (3.2f ) was used to estimate the wear coefficient,
k. The average of a series of repeatable tests yielded kZ1.01!10K4. For
same metals under poor lubrication, Rabinowicz (1980) gives kZ1.0!10K4. Note
that the k estimated by equation (3.2f ) arose from measured wear, temperatures
and forces; Rabinowicz’s k, calculated via Archard’s wear law (1953), arose from
measured wear, forces and distance. Additional tests show similar results with
remarkable accuracy when compared to published wear coefficients. These
experiments reveal that wear (a measure of material degradation) and entropy
are intimately related, and the relationship between entropy and temperature can be
put to use for prediction of material degradation.
4. Discussion
in §2b, equations (2.3) and (2.4) have common rate factors Jij Z vzji =vt that depend
on system parameters zji . If the flow rates Jij are judiciously chosen, then the rate of
degradation dw/dt in equation (2.3) can be observed without waiting for long times.
Equations (2.3)–(2.7) suggest that one can conduct an accelerated failure testing
scheme by increasing process rates Jij while maintaining ‘equivalent’ forces Xij and
Yij to obtain the same sequence of physical processes, in identical proportions, but
with a higher rate. Simply increasing rates Jij may alter the physical processes (Ling
et al. 1997). For example, moderate heat hatches an egg; if heating is accelerated
without maintaining equivalent forces, the egg cooks. Via equation (2.5), altering
any Jij could change every Xij .
As an example, to accelerate wear testing, equations (3.2a) and (3.2b) suggest
increasing sliding (rubbing or slip) speed JZdx/dt while maintaining equivalent
thermodynamic force X and degradation force Y. Higher dx/dt will accelerate wear,
but higher temperatures from friction heat will affect constancy of XZFm/T via
contact temperature T, and YZBmN/T through dependencies of B and possibly
m, on T. This suggests adjusting the normal force N and temperature T, to
compensate and maintain equivalent Y.
5. Concluding remarks
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